JP5865208B2 - Mold manufacturing method - Google Patents

Description

  The present invention relates to a method for producing a mold having a fine concavo-convex pattern on the surface and a mold produced using the method.

  In nanoimprinting, a mold (generally referred to as a mold, stamper, or template) in which a concavo-convex pattern is formed is pressed (imprinted) against a resist applied on a substrate to be transferred, and the resist is mechanically deformed or fluidized to make fine patterns. This is a technology that precisely transfers a pattern to a resist film. Once a mold is made, it is economical because nano-level microstructures can be easily and repeatedly molded, and it is a transfer technology with little harmful waste and emissions. Application to is expected.

  A mold having a mesa structure including a mesa portion (a portion whose upper surface is relatively flat and higher than the surroundings) and a flange portion around the mesa portion (hereinafter also referred to as a mesa mold) is known (for example, Patent Document 1). When nanoimprinting is performed using a mesa mold, the contact area between the mold and the resist is reduced compared to when a flat mold is used, and the mold can be removed from the resist with a small force. is there. For example, when a pattern is repeatedly transferred (step-and-repeat) to the same substrate to be transferred, a mesa mold is used to transfer the next pattern to the mold first. There is also an advantage that the previously transferred pattern can be prevented from being damaged due to interference with the transferred pattern.

  By the way, the mold may be provided with auxiliary marks such as an alignment mark and an identification mark in addition to the uneven pattern to be transferred such as a semiconductor circuit pattern and a surface processing pattern.

  Conventionally, as a method of manufacturing a mold having such an auxiliary mark, for example, methods of Patent Documents 2 to 4 are known. Patent Document 2 discloses a method of marking an identification mark on a mold using a laser processing machine. Patent Document 3 uses a flat master mold having a fine concavo-convex pattern and auxiliary marks and a flat substrate to be transferred, and passes through the steps of applying resist to the substrate to be transferred, nanoimprinting, and etching. A method for transferring an auxiliary mark to a substrate to be transferred at the same time as an uneven pattern is disclosed. In Patent Document 4, as in Patent Document 3, the auxiliary mark is transferred to a flat transfer substrate simultaneously with the concave-convex pattern, and then a part of the region including the concave-convex pattern is masked and the other region including the auxiliary mark is etched. A method of retreating is disclosed.

  According to the method of Patent Document 4, it is possible to manufacture a mesa mold having a fine concavo-convex pattern on a mesa portion and an auxiliary mark on a flange portion.

JP 2009-170773 A Japanese Patent Application Laid-Open No. 2011-0666153 JP 2011-063004 A JP 2011-066238 A

  However, in the method of Patent Document 4, since the auxiliary mark is fixed to the master mold, the auxiliary mark cannot be easily changed. Thereby, for example, even when a plurality of molds are duplicated from one master mold, the identification mark cannot be changed for each duplicated mold. Further, in the method of Patent Document 4, it is difficult to completely maintain the shape of the auxiliary mark during the process of etching other regions including the auxiliary mark, and the function as the auxiliary mark may be impaired.

  On the other hand, as a method of manufacturing a mesa mold having an auxiliary mark, a mesa mold having a fine uneven pattern on the mesa portion is manufactured, and then, as in Patent Document 2, the auxiliary mark is applied to the flange portion by laser or the like. A method of engraving with is also conceivable. However, in such a method, each mold must be marked, which is inefficient as a manufacturing process.

  The present invention has been made in view of the above problems, and in the manufacture of a mesa mold having an auxiliary mark, it is possible to flexibly cope with the change of the auxiliary mark and to manufacture the mold that can be manufactured more efficiently. It is an object to provide a method and a mold manufactured using the method.

In order to solve the above problems, a mold manufacturing method according to the present invention includes:
In the method for producing a mold having a fine uneven pattern and an auxiliary mark on the surface,
Using a transfer substrate having a mesa structure including a mesa portion and a flange portion,
A plurality of droplets made of curable resin are arranged on the mesa portion by a droplet discharge method, and a plurality of droplets made of curable resin are placed on the flange portion. Arranged so that each droplet is lower than the height of the mesa portion and a plurality of droplets arranged on the flange portion display auxiliary marks,
Curing the curable resin on the mesa part with the concave and convex pattern of the master mold pressed against the plurality of droplets arranged on the mesa part, curing the curable resin on the flange part,
The transferred substrate is etched using the cured curable resin as a mask.

  In the mold manufacturing method according to the present invention, the contact area between the droplets and the droplets arranged on the flange portion is the liquid per droplet arranged on the mesa portion. The plurality of droplets are preferably arranged so as to be larger than the contact area between the droplets and the mesa portion.

  In the mold manufacturing method according to the present invention, the plurality of droplets are arranged on the flange portion so that the width of each contact surface between the droplet and the flange portion is 50 to 500 μm. It is preferable.

  In the mold manufacturing method according to the present invention, the amount of droplets per droplet disposed on the flange portion is larger than the amount of droplets per droplet disposed on the mesa portion. Thus, it is preferable to arrange the plurality of droplets.

  Moreover, in the mold manufacturing method according to the present invention, it is preferable to use a substrate having a wettability of the flange portion surface larger than that of the mesa portion surface as the transfer substrate. In this case, it is preferable to increase the wettability of the flange portion by a method of performing ultraviolet ozone treatment only on the flange portion or a method of forming a thin film having high affinity with the curable resin.

  Further, in the mold manufacturing method according to the present invention, the plurality of droplets may be arranged such that the height of the droplets disposed on the flange portion is larger than the height of the droplets disposed on the mesa portion. It is preferable to perform the arrangement.

  In the mold manufacturing method according to the present invention, it is preferable that the plurality of droplets are arranged on the mesa portion and the plurality of droplets are arranged on the flange portion at the same time.

  In the mold manufacturing method according to the present invention, the etching is preferably performed so that the curable resin on the mesa portion is removed and the curable resin on the flange portion remains. In this case, the auxiliary mark can be contrasted by the difference in optical characteristics between the transfer substrate and the curable resin.

  Alternatively, in the mold manufacturing method according to the present invention, the flange portion of the substrate to be transferred has a metal-containing film on at least a part of the surface of the flange portion, and the plurality of droplets are arranged on the flange portion. Is preferably performed on the metal-containing film. In this case, the auxiliary mark can be contrasted by the difference in optical characteristics between the transfer substrate and the metal-containing film. In this case, the metal-containing film preferably has a fine uneven structure. Further, the mesa portion of the substrate to be transferred has a metal-containing film on the surface of the mesa portion, and after etching, the metal-containing film in the mesa portion is removed using the curable resin or the metal-containing film as a mask and the flange portion. The transferred substrate is preferably etched so that the metal-containing film remains.

  The mold according to the present invention is manufactured by the method described above.

  The mold manufacturing method according to the present invention, in particular, arranges droplets of a curable resin by a droplet discharge method so as to display an auxiliary mark, and then etches the cured curable resin as a mask. Even if it is desired to change the auxiliary mark, the auxiliary mark can be easily changed by simply changing the design of the arrangement position of the droplets. As a result, in the production of a mesa mold having an auxiliary mark, it is possible to flexibly cope with the change of the auxiliary mark, and it is possible to manufacture more efficiently.

It is the schematic which shows the example of the mesa type | mold mold which has a fine uneven | corrugated pattern and an auxiliary | assistant mark. It is the schematic which shows the example of an identification mark. It is a schematic sectional drawing which shows the process of the manufacturing method of the mold which concerns on 1st Embodiment. It is a schematic sectional drawing which shows the process of the manufacturing method of the mold which concerns on 2nd Embodiment. It is the schematic which shows the design change in 2nd Embodiment. It is the schematic which shows the design change in 3rd Embodiment.

  Hereinafter, although an embodiment of the present invention is described using a drawing, the present invention is not limited to this. In addition, for easy visual recognition, the scale of each component in the drawings is appropriately changed from the actual one.

"Mesa mold with auxiliary marks"
First, the mold obtained by the present invention will be briefly described. FIG. 1 is a schematic view showing an example of a mesa mold having a fine uneven pattern and auxiliary marks. Specifically, FIG. 1 a is a top view of the mold 1, and FIG. 1 b is a front view of the mold 1. FIG. 2 is a schematic diagram illustrating an example of an identification mark.

  According to the manufacturing method of the present invention, for example, a mesa mold 1 as shown in FIG. 1 is manufactured. The mold 1 has a mesa structure including a mesa portion 2 and a flange portion 3, and the upper surface 2s of the mesa portion 2 is higher than the upper surface 3s of the flange portion 3 by a level difference h (FIG. 1b). The fine uneven pattern 21 is formed on the upper surface 2 s of the mesa portion 2, and the auxiliary mark is formed on the upper surface 3 s of the flange portion 3.

  The auxiliary mark is a pattern that performs an auxiliary function, such as an alignment mark or an identification mark, in the nanoimprint using the mold 1 that is not a transfer target. The alignment mark is a pattern for assisting the position adjustment of the mold during imprinting, and the identification mark is a pattern for identifying and managing individual molds. The identification mark displays mold management information by, for example, characters, figures, symbols, images, barcodes, bit recording patterns, or combinations thereof. Management information includes, for example, mold manufacturing number, management number, manufacturing conditions (manufacturing date, temperature, master type), specifications (thickness, flatness, parallelism, uneven pattern information, uneven pattern placement coordinates), usage history Etc. The auxiliary mark may be composed of one or more lines, or may be composed of an array of a plurality of dots as shown in FIG. The auxiliary mark can be detected by visual observation, microscope observation, laser measurement, image recognition processing using an electronic computer, or the like.

  The auxiliary mark may be displayed by the uneven shape of the upper surface 3s itself of the flange portion 3, or may be displayed by a pattern of a material different from the material constituting the flange portion 3 (or mold 1), such as a curable resin or metal. Also good. In this manner, by patterning a material different from the material constituting the flange portion 3 (or the mold 1) on the upper surface 3s of the flange portion 3, the contrast is improved and information can be easily read. The size (for example, the size per character and figure) of the auxiliary mark is not particularly limited, but is appropriately selected within a range from, for example, a μm scale to a mm scale depending on the detection method. A specific method of forming the auxiliary mark will be described in detail in each embodiment described later.

  If the auxiliary mark is no longer needed, it can be removed. For example, when the auxiliary mark is displayed with a curable resin, the auxiliary mark is displayed with a pattern of a material containing metal by oxygen ashing, ultraviolet (UV) ozone treatment cleaning, and cleaning with acid or alkali. In some cases, the auxiliary mark can be removed by washing with acid or alkali.

“First Embodiment”
A manufacturing method of a mold 1 and a first embodiment of a mold manufactured by the method will be described. FIG. 3 is a schematic cross-sectional view showing a process of the mold manufacturing method according to the first embodiment.

  As shown in FIG. 3, the manufacturing method of the mold 1 of the present embodiment is an inkjet apparatus (shown) including a transfer substrate 5 (FIG. 3a) having a mesa structure including a mesa portion 5a and a flange portion 5b and an inkjet head 40. And a plurality of droplets 41 made of the curable resin are arranged on the mesa portion 5a, and the plurality of droplets 42 made of the same curable resin are placed on the flange portion 5b by the inkjet method. The plurality of droplets 42 disposed on 5b are arranged such that the height of each of the droplets 42 is lower than the height of the mesa portion 5a and the plurality of droplets 42 disposed on the flange portion 5b display the auxiliary mark 30 ( 3B), the curable resin on the mesa portion 5a and the flange portion 5b in a state where the concave and convex pattern 43a of the master mold 43 is pressed against the plurality of droplets 41 arranged on the mesa portion 5a. The curable resin is cured (FIG. 3c), and the curable resin 44 on the mesa portion 5a is removed and the curable resin 45 on the flange portion 5b remains using the cured curable resins 44 and 45 as a mask. Then, the transferred substrate 5 is etched so as to become (FIGS. 3d and e). After the etching is completed, for example, a mold 1 (that is, a master disk 43) as shown in FIG. 3e can be obtained. In the present embodiment, the visibility of the auxiliary mark 30 is exhibited mainly by the curable resin 45 remaining on the flange portion 5b.

(Transfer substrate)
The transferred substrate 5 is a substrate that is the basis of the mold 1. In the present invention, in order to manufacture the mesa mold 1, a mesa structure having a mesa portion 5 a and a flange portion 5 b is formed in advance on the transfer substrate 5. Due to this mesa structure, at the time of imprinting by the master mold 43 (FIG. 3c), only the droplets 41 disposed on the mesa portion 5a of the transfer substrate 5 are in contact with the master mold 43 and disposed on the flange portion 5b. Contact between the droplet 42 and the master mold 43 is avoided. The step h of the mesa portion 5a is preferably 1 to 1000 μm, more preferably 10 to 500 μm, and still more preferably 20 to 100 μm. This is because when the step h is lower than the height of the droplet 42 disposed on the flange portion 5b (in consideration of a general droplet amount, it is approximately 500 nm to several μm), the droplet 42 and the master This is because the mold 43 may come into contact and contaminate the master mold 43. On the other hand, when the level difference h is too high, the distance between the droplet discharge port of the inkjet head 40 and the flange portion upper surface 5d is increased, so that the droplet placement accuracy is deteriorated. The shape of the substrate 5 to be transferred is, for example, a disk shape when the use of the mold 1 is manufacture of an information recording medium.

In the case where the curable resin is photocurable and the master mold does not have optical transparency such as silicon (Si), a quartz substrate is preferable in order to enable exposure to the curable resin. The quartz substrate is appropriately selected according to the purpose without particular limitation as long as it has light transparency and a thickness of 0.3 mm or more. For example, as the substrate 5 to be transferred, a quartz substrate surface covered with an adhesion layer such as a silane coupling agent, or a metal film made of Cr, W, Ti, Ni, Ag, Pt, Au or the like is laminated on the quartz substrate. And those obtained by laminating a metal oxide film made of CrO ₂ , WO ₂ , TiO ₂ or the like on a quartz substrate, or those obtained by coating the surface of the laminate with an adhesion layer such as a silane coupling agent. It is done. In the present embodiment, a case where the transfer substrate 5 does not have a metal-containing film such as the above metal film or metal oxide film will be described. The case where the transfer substrate 5 has a metal-containing film will be described in the second and third embodiments. The adhesion layer is not essential, but is appropriately used for improving the adhesion between the curable resin and the transfer substrate 5. The adhesion layer should just be formed in the pattern formation area (area | region which forms an uneven | corrugated pattern) of the mesa part 5a at least.

  In addition, the above-mentioned “having light transparency” specifically means curing when light is incident from the other surface of the substrate so as to be emitted from one surface on which the curable resin film is formed. This means that the functional resin is sufficiently cured, and at least the transmittance of light having a wavelength of 200 nm or more from the other surface to the one surface is 5% or more.

  The thickness of the quartz substrate is usually preferably 0.3 mm or more. This is because if it is 0.3 mm or less, it is likely to be damaged by pressing during handling or imprinting.

  On the other hand, when the master mold 43 has optical transparency such as quartz, the structure and material of the transfer substrate 5 are not particularly limited and can be appropriately selected according to the purpose. The structure of the transfer substrate 5 may be a single layer structure or a laminated structure as long as it is a mesa structure. The material can be appropriately selected from those known as substrate materials, and examples thereof include silicon, nickel, aluminum, glass, and resin. These board | substrate materials may be used individually by 1 type, and may use 2 or more types together. The transferred substrate 5 may be appropriately synthesized or a commercially available product may be used. Moreover, what coat | covered the surface with the silane coupling agent may be used.

  The thickness of the transfer substrate 5 (the total thickness of the mesa portion) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.05 mm or more, more preferably 0.1 mm or more. . If the thickness of the substrate is less than 0.05 mm, the substrate may be bent during imprinting, and a uniform contact state may not be ensured.

(Curable resin)
The curable resin is not particularly limited, but in this embodiment, for example, it is prepared by adding a photopolymerization initiator (about 2% by mass) and a fluorine monomer (0.1 to 1% by mass) to the polymerizable compound. Materials can be used.

  Moreover, antioxidant (about 1 mass%) can also be added as needed. The material prepared by the above procedure can be cured by, for example, ultraviolet light having a wavelength of 360 nm. For those having poor solubility, it is preferable to add a small amount of acetone or ethyl acetate for dissolution, and then distill off the solvent.

Examples of the polymerizable compound include benzyl acrylate (Biscoat (registered trademark) # 160: manufactured by Osaka Organic Chemical Co., Ltd.), ethyl carbitol acrylate (Biscoat (registered trademark) # 190: manufactured by Osaka Organic Chemical Co., Ltd.), polypropylene glycol di In addition to acrylate (Aronix (registered trademark) M-220: manufactured by Toagosei Co., Ltd.), trimethylolpropane PO-modified triacrylate (Aronix (registered trademark) M-310: manufactured by Toagosei Co., Ltd.), etc. The compound A etc. which are represented can be mentioned.
Structural formula 1:

  The polymerization initiator may be 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (IRGACURE®). 379: manufactured by Toyotsu Chemiplus Co., Ltd.) and the like.

Moreover, as said fluorine monomer, the compound B etc. which are represented by following Structural formula 2 etc. can be mentioned.
Structural formula 2:

  For example, the viscosity of the curable resin is 8 to 20 cP, and the surface energy of the curable resin is 25 to 35 mN / m. Here, the viscosity of the curable resin is a value measured at 25 ± 0.2 ° C. using a RE-80L rotational viscometer (manufactured by Toki Sangyo Co., Ltd.). The rotational speed at the time of measurement was 100 rpm when 0.5 cP or more and less than 5 cP, 50 rpm when 5 cP or more and less than 10 cP, 20 rpm when 10 cP or more and less than 30 cP, and 10 rpm when 30 cP or more and less than 60 cP. The surface energy of the curable resin is “UV nanoimprint materials: Surface energies, residual layers, and imprint quality”, H. Schmitt, L. Frey, H. Ryssel, M. Rommel, C. Lehrer, J. Vac. Sci. Technol. B, Volume 25, Issue 3, 2007, Pages 785-790. Specifically, the surface energy of a silicon substrate that has been subjected to UV ozone treatment and a silicon substrate that has been surface-treated with Optool (registered trademark) DSX (manufactured by Daikin Corporation) is obtained, and the contact angle of the curable resin to both substrates is determined. The surface energy of the curable resin was calculated.

  The curable resin disposed on the mesa portion 5a and the curable resin disposed on the flange portion 5b may be the same material or different materials.

(Disposition method of droplets made of curable resin)
As a method for arranging droplets made of a curable resin, a droplet discharge method that can arrange a predetermined amount of droplets at a predetermined position on the transfer substrate 5 such as an inkjet method or a dispense method is used. When disposing the droplets on the substrate 5, an ink jet printer or a dispenser may be properly used according to a desired droplet amount (amount per droplet disposed). For example, an ink jet printer is used when the droplet amount is less than 100 nl, and a dispenser is used when the droplet amount is 100 nl or more. In the present embodiment, an ink jet method is used.

  Examples of the inkjet head 40 that discharges droplets from a nozzle include a piezo method, a thermal method, and an electrostatic method. Among these, a piezo method capable of adjusting an appropriate amount of liquid and a discharge speed is preferable. Before arranging the droplets on the substrate 5, the droplet amount and the discharge speed are adjusted in advance. For example, the appropriate amount of liquid is increased at a position on the substrate 5 corresponding to a region where the spatial volume of the concave / convex pattern of the master mold 43 is large, or on the substrate 5 corresponding to a region where the spatial volume of the concave / convex pattern of the master mold 43 is small. It is preferable to adjust the position by decreasing the number. Such adjustment is appropriately controlled according to the discharge amount of the droplets (the amount per droplet when discharged). For example, when an ink jet head having an ejection amount of 1 pl is used and the droplet amount is set to 5 pl, the droplet amount is controlled by ejecting it to the same place five times. The amount of droplets is obtained, for example, by measuring the three-dimensional shape of the droplets discharged on the substrate 5 (or another substrate of the same quality) in advance under the same conditions with a confocal microscope and calculating the volume from the shape. It is done.

  After adjusting the droplet amount as described above, the droplets are arranged on the transfer substrate 5 according to a predetermined droplet arrangement pattern. The droplet arrangement pattern is configured by two-dimensional coordinate information including a lattice point group corresponding to the droplet arrangement. This droplet arrangement pattern is designed based on the imprint conditions and the shape and size of the auxiliary mark.

  The arrangement of the droplets 42 on the flange portion 5b is such that the height of each of the plurality of droplets 42 arranged on the flange portion 5b is lower than the height of the mesa portion 5a and the plurality of droplets 42 arranged on the flange portion 5b. The droplet 42 is displayed so as to display the auxiliary mark. Since the height of each of the plurality of droplets 42 is lower than the height of the mesa portion 5a, the droplets 42 can be prevented from adhering to the master mold 43 during imprinting by the master mold 43. When the master mold 43 also has a mesa structure, it is considered that the possibility that the droplets 42 adhere to the master mold 43 is reduced. However, for example, when the master mold 43 is translated in order to adjust the position (a movement in which the distance from the transfer substrate 5 is kept constant), such a problem of adhesion of droplets remains. Therefore, regardless of the shape of the master mold 43, the height of each of the plurality of droplets 42 is preferably lower than the height of the mesa portion 5a as in the present invention. In the present invention, since the shape of the auxiliary mark 30 is displayed by the plurality of droplets 42, the auxiliary mark 30 can be flexibly changed by changing the arrangement of the droplets.

  As described above, the auxiliary mark may be displayed by a line in which a plurality of droplets are combined, or may be displayed by an arrangement of droplets (dots). Actually, since the etching process is performed, the shape of the auxiliary mark displayed by the droplet may not necessarily match the final shape of the auxiliary mark 30. That is, the final line of the auxiliary mark 30 becomes thinner or the dot becomes smaller. Therefore, when displaying the auxiliary mark with the droplet, in consideration of the above, for example, the amount of the droplet is increased or the line is thickened so that the information transmission function of the auxiliary mark 30 is not impaired by the etching process. There is a need to.

  The droplet arrangement on the mesa portion 5a and the droplet arrangement on the flange portion 5b may be performed simultaneously or separately. Here, performing these droplet arrangements “simultaneously” means that the droplet arrangement on the mesa 5a and the droplet arrangement on the flange 5b within a one-way scan of a droplet discharge unit such as an inkjet head. And “separately” performing these droplet arrangements means that only the droplet arrangement on the mesa unit 5a and the scanning to the flange unit 5b are performed in the scanning movement of the droplet discharge unit. This means that the scanning that only performs droplet placement is completely separated. Furthermore, each of these droplet arrangements can be performed using different ink jet heads. However, with respect to the arrangement of the droplets on the mesa portion 5a and the flange portion 5b, if different curable resins and different inkjet heads are used, the time required for the droplet arrangement increases, so the same curable resin and the same inkjet head are used. Most preferably, droplets are placed simultaneously using

  In the present invention, from the viewpoint of improving the visibility of the auxiliary mark 30, the contact area between the droplet 42 per droplet disposed on the flange portion 5b and the flange portion 5b (that is, the upper surface 5d of the flange portion 5b). Of the area where one droplet 42 is in contact with each other) is the contact area between the droplet 41 and the mesa portion 5a arranged on the mesa portion 5a (that is, the mesa portion). The plurality of droplets are preferably arranged so as to be larger than the average area of the area of the upper surface 5c of 5a in contact with one droplet 41). This is due to the following reason. As a simple method of arranging the droplets, the droplet arrangement on the mesa portion 5a and the droplet arrangement on the flange portion 5b are the same except for the droplet arrangement pattern (for example, the material of the droplet). , Discharge amount, droplet amount, surface energy, etc.). However, since the conditions for arranging the droplets on the mesa portion 5a are often determined by the relationship with the imprint by the master mold 43, when such a method is performed, the droplets on the flange portion 5b are used. The arrangement condition necessarily depends on the condition of the droplet arrangement on the mesa portion 5a. By the way, in the droplet arrangement on the mesa portion 5a, it is required to arrange small droplets at high density from the viewpoint of preventing unfilled defects of the curable resin film during imprinting. Therefore, if the condition of the droplet arrangement on the flange portion 5b is subordinate to the condition of the droplet arrangement on the mesa portion 5a, there is a possibility that only an auxiliary mark with a thin line can be displayed. This greatly affects the visibility of the auxiliary mark 30 of the finished mold 1. Therefore, from the viewpoint of improving the visibility of the auxiliary mark 30, as one guideline, the contact area of the droplet 42 on the flange portion 5 b is made larger than the contact area of the droplet 41 on the mesa portion 5 a.

  In addition, the contact area of the droplet per droplet means the contact area when the droplet is in a single state (that is, a state where it is not combined with other droplets). Therefore, when the shape of the auxiliary mark is displayed by a line in which a plurality of droplets are combined, the contact area is assumed when such a state is assumed, and this can be confirmed by a preliminary test. Further, when a plurality of droplets are ejected to the same place, the whole is considered as one droplet.

  As a method for increasing the contact area of the droplet 42 on the flange portion 5b in this way, for example, the droplet amount per droplet disposed on the flange portion 5b is set to the droplet disposed on the mesa portion 5a. A method of increasing the amount of droplets per droplet can be mentioned. The method for adjusting the droplet amount is as described above. Alternatively, by using the transfer substrate 5 in which the wettability of the upper surface 5d of the flange portion with respect to the droplet 42 on the flange portion 5b is larger than the wettability of the upper surface 5c of the mesa portion with respect to the droplet 41 on the mesa portion 5a. Thus, the contact area of the droplet 42 can be increased. This is because when the wettability is larger (that is, the surface energy of the flange portion upper surface 5d is larger or the contact angle of the droplet is smaller), the contact area is expanded due to the effect of wetting and spreading even with the same droplet amount. For example, the wettability of the flange portion 5b is increased by a surface treatment method such as performing UV ozone treatment only on the flange portion 5b or forming a thin film (for example, an organic molecular film) having high affinity with the curable resin. can do.

  Furthermore, from the viewpoint of easily confirming the auxiliary mark with the naked eye, the width of the contact surface between the droplet 42 and the flange portion 5b for each droplet (the diameter when the droplet is approximated by a circle) is 50 to 500 μm. Thus, it is preferable to arrange the droplets 42 on the flange portion 5b.

  On the other hand, it is also effective to arrange the droplets so that the height of the droplets 42 arranged on the flange portion 5b is larger than the height of the droplets 41 arranged on the mesa portion 5a. The height of the droplet can also be controlled by changing the wettability (surface energy) of the transfer substrate 5. For example, when the surface energy of the mesa portion upper surface 5c is increased, the wettability is improved and the droplet height is decreased. In order to increase the surface energy, only the mesa portion 5a is activated by UV ozone treatment or the like, or a thin film (for example, an organic molecular film) having a high affinity with the curable resin is formed only on the mesa portion 5a. There is a way. The height of the droplet 42 can also be increased by increasing the amount of the droplet 42 disposed on the flange portion 5b.

  When performing different surface treatments on the mesa portion 5a and the flange portion 5b, a method of protecting either surface with a surface protection tape is preferable. The surface protective tape is not particularly limited as long as it is a commercially available protective tape for semiconductor wafers. Since there is a concern of adhesive residue when the surface protection tape is peeled off, a method of attaching the surface protection tape to the flange portion 5b is more preferable than on the mesa portion 5a to be imprinted. In a state where the surface protective tape is locally attached, the surface that is not protected by means such as UV ozone cleaning, spin coating, dip coating, spray coating, or vapor deposition is surface treated. After the surface treatment, the surface protective tape is peeled off, so that different surface treatments are performed on the mesa portion 5a and the flange portion 5b.

(Master mold)
The master mold 43 used in the present embodiment can be manufactured by the following procedure, for example. First, a PHS (polyhydroxy styrene) -based chemically amplified resist, a novolac-based resist, an acrylic resin such as PMMA (polymethyl methacrylate), etc., as a main component is applied onto a silicon substrate by spin coating, A resist layer is formed. Thereafter, the silicon substrate is irradiated with laser light (or electron beam) while being modulated corresponding to the desired concavo-convex pattern, and the concavo-convex pattern is exposed on the surface of the resist layer. Thereafter, the resist layer is developed, and selective etching is performed by RIE (reactive ion etching) using the removed resist layer pattern as a mask to obtain a silicon mold having a predetermined uneven pattern.

  In the present embodiment, the case where a silicon mold is used will be described. However, the master mold 43 is not limited to this, and a quartz mold can also be used. In this case, the quartz mold can be manufactured by a method similar to the manufacturing method of the silicon mold, a replication method of the silicon mold, or the like. The master mold 43 may also have a mesa structure.

  The shape of the concave / convex pattern 43a of the master mold 43 is not particularly limited, and is appropriately selected according to the use of nanoimprint. For example, a typical pattern is a line & space pattern. And the length of the convex part of a line & space pattern, the width | variety of a convex part, the space | interval of convex parts, and the height (the depth of a recessed part) of a convex part from a recessed part bottom face are set suitably. For example, the width of the convex portion is 10 to 100 nm, more preferably 20 to 70 nm, the interval between the convex portions is 10 to 500 nm, more preferably 20 to 100 nm, and the height of the convex portion is 10 to 500 nm. Preferably it is 30-100 nm. Moreover, the shape of the convex part which comprises the uneven | corrugated pattern 43a may be the shape where the dot which has cross sections, such as a rectangle, a circle | round | yen, and an ellipse, arranged.

(Release agent)
In the present invention, it is preferable to perform a release treatment on the surface of the master mold 43 in order to improve the release property between the curable resin and the master mold 43. As a mold release agent used for the mold release treatment, Opkin (registered trademark) DSX manufactured by Daikin Industries, Ltd., Novec (registered trademark) EGC-1720 manufactured by Sumitomo 3M Co., Ltd., and the like are used as fluorine-based silane coupling agents. .

  In addition, known fluorine resins, hydrocarbon lubricants, fluorine lubricants, fluorine silane coupling agents, and the like can be used.

  For example, PTFA (polytetrafluoroethylene), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene copolymer), ETFE (tetrafluoroethylene Ethylene copolymer).

  For example, hydrocarbon lubricants include carboxylic acids such as stearic acid and oleic acid, esters such as butyl stearate, sulfonic acids such as octadecyl sulfonic acid, phosphate esters such as monooctadecyl phosphate, stearyl alcohol and oleyl Examples thereof include alcohols such as alcohol, carboxylic acid amides such as stearamide, and amines such as stearylamine.

  For example, examples of the fluorine-based lubricant include a lubricant in which part or all of the alkyl group of the hydrocarbon-based lubricant is substituted with a fluoroalkyl group or a perfluoropolyether group.

For example, as the perfluoropolyether group, perfluoromethylene oxide polymer, perfluoroethylene oxide polymer, perfluoro-n-propylene oxide polymer (CF ₂ CF ₂ CF ₂ O) _n , perfluoroisopropylene oxide polymer ( CF (CF ₃ ) CF ₂ O) _n or a copolymer thereof. Here, the subscript n represents the degree of polymerization.

For example, the fluorinated silane coupling agent has at least 1, preferably 1 to 10, alkoxysilane groups and chlorosilane groups in the molecule, and preferably has a molecular weight of 200 to 10,000. For example, the alkoxysilane group, -Si _{(OCH 3)} 3 _{group, -Si (OCH 2 CH 3)} 3 group. Examples of the chlorosilane group, and a -Si _{(Cl) 3} group. Specifically, heptadecafluoro-1,1,2,2-tetra-hydrodecyltrimethoxysilane, pentafluorophenylpropyldimethylchlorosilane, tridecafluoro-1,1,2,2-tetra-hydrooctyltriethoxy Compounds such as silane and tridecafluoro-1,1,2,2-tetra-hydrooctyltrimethoxysilane.

(Imprint method)
Before contacting the master mold 43 and the curable resin, the residual gas is reduced by reducing the atmosphere between the master mold 43 and the substrate 5 to a reduced pressure or vacuum atmosphere. However, in a high vacuum atmosphere, the curable resin before curing volatilizes, and it may be difficult to maintain a uniform film thickness. Therefore, the residual gas is preferably reduced by setting the atmosphere between the master mold 43 and the substrate 5 to a He atmosphere or a reduced pressure He atmosphere. Since He permeates the quartz substrate, the trapped residual gas (He) gradually decreases. Since it takes time to transmit He, it is more preferable to use a reduced pressure He atmosphere. The reduced pressure atmosphere is preferably 1 to 90 kPa, and particularly preferably 1 to 10 kPa.

  The pressing pressure of the master mold 43 is performed in the range of 100 kPa or more and 10 MPa or less. When the pressure is higher, the flow of the curable resin is promoted, and the compression of the residual gas, the dissolution of the residual gas in the curable resin, and the permeation of He in the quartz substrate are promoted, leading to an improvement in the removal rate. However, if the applied pressure is too strong, there is a possibility that the master mold 43 and the substrate 5 may be damaged when foreign matter is caught when the master mold 43 comes into contact. Therefore, the pressing pressure of the master mold 43 is preferably 100 kPa or more and 10 MPa or less, more preferably 100 kPa or more and 5 MPa, and further preferably 100 kPa or more and 1 MPa or less. The reason why the pressure is set to 100 kPa or more is that when imprinting is performed in the atmosphere, when the space between the master mold 43 and the substrate 5 is filled with liquid, the pressure between the master mold 43 and the substrate 5 is increased at atmospheric pressure (about 101 kPa). This is because.

  The exposure of the curable resin on the mesa portion 5a is performed in a state where the concave / convex pattern 43a of the master mold 43 is pressed against the droplets 41 arranged on the mesa portion 5a. Thereby, the droplet 41 becomes a curable resin film to which the concave / convex pattern 43a is transferred. The curable resin on the flange portion 5b is also cured by exposure to basically the shape when the droplets are arranged. At this time, the exposure of the mesa portion 5a and the flange portion 5b may be performed simultaneously or separately.

  After the master mold 43 is pressed to form a curable resin film, the peeling is performed, for example, by holding the outer edge of either the master mold 43 or the substrate 5 and sucking the back surface of the other substrate 5 or the master mold 43. There is a method of peeling by holding the outer edge holding part or the rear surface holding part relative to the direction opposite to the pressing in the held state.

(etching)
Etching of the transfer substrate 5 is performed using the cured curable resins 44 and 45 as a mask. As a result, a pattern corresponding to the concavo-convex pattern of the master mold 43 is formed on the mesa portion upper surface 5 c of the transferred substrate 5, and the auxiliary mark 30 is formed on the flange portion upper surface 5 d of the transferred substrate 5. Further, in this embodiment, etching is performed so that the curable resin 44 on the mesa portion 5a is removed and the curable resin 45 on the flange portion 5b remains (FIG. 3e). By leaving the curable resin on the auxiliary mark 30, the contrast is improved due to the difference in optical characteristics between the substrate to be transferred and the curable resin, and the visibility of the auxiliary mark 30 is improved. Usually, the film thickness of the imprinted curable resin 44 (the thickness of the entire protrusion including the so-called remaining film portion) is smaller than 1 μm. Therefore, if the height of the curable resin 45 is adjusted to be larger than the film thickness of the curable resin 44, the above state can be realized at the timing of the end of etching. For example, an appropriate etching time can be obtained in consideration of the film thickness of the curable resin 44 obtained in advance on a trial basis, the height of the curable resin 45, the etching rate of the curable resins 44 and 45, and the like. it can. It is also possible to realize the above state by making the curable resins disposed in the mesa portion 5a and the flange portion 5b different from each other and making a difference in the etching rate.

  Etching is not particularly limited as long as it can form a concavo-convex pattern on the substrate, and can be appropriately selected according to the purpose. Examples thereof include ion milling, reactive ion etching (RIE), and sputter etching. Can be mentioned. Among these, ion milling and RIE are particularly preferable.

  The ion milling method is also called ion beam etching and introduces an inert gas such as Ar into an ion source to generate ions. This is accelerated through the grid, and collides with the sample substrate for etching. Examples of the ion source include a Kaufman type, a high frequency type, an electron impact type, a duoplasmatron type, a Freeman type, an ECR (electron cyclotron resonance) type, and the like.

  Ar gas can be used as a process gas in ion beam etching, and fluorine-based gas or chlorine-based gas can be used as an etchant for RIE.

  As described above, in the mold manufacturing method of the present embodiment, the curable resin droplets are arranged by the droplet discharge method so as to display the auxiliary marks, and then the curable resin is etched as a mask. Even if it is desired to change the auxiliary mark every time, the auxiliary mark can be easily changed only by changing the design of the arrangement position of the droplets. As a result, in the production of a mesa mold having an auxiliary mark, it is possible to flexibly cope with the change of the auxiliary mark, and it is possible to manufacture more efficiently.

<Design changes>
If the above embodiment is applied, even if the auxiliary mark once formed is removed, the droplet of the curable resin is disposed again only on the flange portion, and the curable resin is cured to form the auxiliary mark 30. can do. That is, in the mold 1 manufactured by the manufacturing method of the present invention, information can be updated by erasing and adding the auxiliary mark 30.

  In the above embodiment, etching is performed so that the curable resin 44 on the mesa portion 5a is removed and the curable resin 45 on the flange portion 5b remains, but even if all the curable resin is removed. Good. In this case, the auxiliary mark 30 is displayed by the unevenness of the flange portion itself.

  In the above embodiment, the case where the curable resin has photocurability has been described, but the present invention is not limited thereto. That is, in this invention, it is also possible to use a thermosetting resin, for example.

  Note that the method of displaying the auxiliary marks with droplets can be applied to a flat transfer substrate having no mesa structure, if a master mold having a mesa structure is used.

“Second Embodiment”
Next, a second embodiment of the mold manufacturing method will be described. FIG. 4 is a schematic cross-sectional view showing the steps of the mold manufacturing method according to the present embodiment. This embodiment is different from the first embodiment in that only the flange portion 5b of the transfer substrate 5 has the metal-containing film 6 on the surface thereof. Therefore, a detailed description of the same configuration as that of the first embodiment is omitted unless particularly required.

  As shown in FIG. 4, the manufacturing method of the mold 1 of the present embodiment has a mesa structure including a mesa portion 5a and a flange portion 5b, and the flange portion 5b has a metal-containing film 6 on the surface thereof. 5 (FIG. 4a) and an inkjet apparatus (not shown) including an inkjet head 40, a plurality of droplets 41 made of a curable resin are arranged on the mesa portion 5a by an inkjet method, and the flange portion 5b is placed on the flange portion 5b. A plurality of droplets 42 made of the same curable resin are arranged such that the height of each of the plurality of droplets 42 disposed on the flange portion 5b is lower than the height of the mesa portion 5a and the plurality of droplets 42 disposed on the flange portion 5b. The droplet 42 is arranged so as to display the auxiliary mark 30 (FIG. 4b), and the concave / convex pattern 43a of the master mold 43 is pressed against the plurality of droplets 41 arranged on the mesa portion 5a. Then, the curable resin on the mesa portion 5a and the curable resin on the flange portion 5b are cured (FIG. 4c), and the curable resin 44 on the mesa portion 5a is removed using the cured curable resins 44 and 45 as a mask. In addition, the transfer substrate 5 is etched so that the curable resin 45 on the flange portion 5b remains (FIGS. 4d and e), and then the curable resin 45 remaining on the flange portion 5b is removed ( FIG. 4f). After the removal of the curable resin, for example, a mold 1 as shown in FIG. 4f (that is, a double plate of the master mold 43) can be obtained. In the present embodiment, the visibility of the auxiliary mark 30 is exhibited mainly by the metal-containing film 6 patterned on the flange portion 5b.

(Metal-containing film)
The metal-containing film is a film composed of a material mainly containing a metal such as a metal or a metal compound. The “main component” means that the composition ratio in the material is 50% by mass or more. By displaying the auxiliary mark 30 with the metal-containing film 6 as in the present embodiment, the visibility of the auxiliary mark is improved. From the viewpoint of improving visibility, the reflectance of the metal-containing film is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more at a wavelength of 365 nm. The thickness of the metal-containing film is usually 2 to 30 nm, preferably 5 to 20 nm. In particular, when the thickness exceeds 30 nm, the UV transmittance is lowered, and the curing failure of the curable resin is likely to occur. The metal-containing film can be formed by a film forming method such as a vacuum evaporation method or a sputtering method. Examples of the material for the metal-containing film include Cr, W, Ti, Ni, Ag, Pt, Au, CrO ₂ , WO ₂ , and TiO ₂ . In addition, the metal containing film 6 should just comprise the surface which will form the auxiliary mark 30 at least among the flange part upper surfaces 5d.

  In addition, when it is desired to form an auxiliary mark including a fine pattern exceeding the resolution of the droplet arrangement drawing, the identification mark may be formed by combining the pattern formed by a general photolithography technique and the droplet arrangement pattern. . For example, FIG. 5 is a schematic view showing a manufacturing process in the case where the metal-containing film 6 has a concavo-convex structure finer than the size of a droplet. In FIG. 5, for example, the black portion of the metal-containing film 6 represents a convex portion, and the white portion represents a concave portion. The fine uneven structure of the metal-containing film 6 is formed in advance by, for example, a photolithography technique. In this case, after the droplet 41 is disposed on the mesa portion 5a of the transfer substrate 5 and the droplet 42 is disposed on the flange portion 5b (FIG. 5b), the process proceeds to the etching step. As a result, an auxiliary mark 30 having a fine uneven structure as shown in FIG. 5c is formed.

(Method for removing curable resin)
As the method for removing the curable resin, for example, from the state of FIG. 4e, a wet process such as cleaning in an acid or alkali can be adopted, and a dry process such as UV ozone treatment or oxygen ashing can also be adopted. .

  As described above, the mold manufacturing method of the present embodiment also etches using the curable resin as a mask after disposing the curable resin droplets by the droplet discharge method so as to display the auxiliary marks. The same effects as those of the first embodiment are obtained.

  Furthermore, in this embodiment, since an auxiliary mark is displayed by the metal containing film patterned on the flange part 5b, visibility can be improved.

  Furthermore, when the metal-containing film has a concavo-convex structure finer than the size of the droplet, an auxiliary mark including a fine pattern exceeding the resolution of the droplet arrangement drawing can be formed.

“Third Embodiment”
Next, a third embodiment of the mold manufacturing method will be described. FIG. 6 is a schematic cross-sectional view showing the steps of the mold manufacturing method according to the present embodiment. This embodiment differs from the second embodiment in that the mesa portion 5a of the transfer substrate 5 also has a metal-containing film 6 on its surface. Therefore, a detailed description of the same configuration as in the first and second embodiments is omitted unless particularly required.

  As shown in FIG. 6, the manufacturing method of the mold 1 of this embodiment has a mesa structure including a mesa portion 5a and a flange portion 5b, and the mesa portion 5a and the flange portion 5b have a metal-containing film 6 on the surface thereof. A plurality of droplets 41 made of a curable resin are arranged on the mesa portion 5a by an ink jet method using the substrate to be transferred 5 (FIG. 6a) and an ink jet apparatus (not shown) including the ink jet head 40, and a flange. A plurality of droplets 42 made of the same curable resin are placed on the flange portion 5b and the height of each of the plurality of droplets 42 placed on the flange portion 5b is lower than the height of the mesa portion 5a. The plurality of droplets 42 arranged so as to display auxiliary marks (FIG. 6b), and the concave / convex pattern 43a of the master mold 43 is formed on the plurality of droplets 41 arranged on the mesa portion 5a. The curable resin on the mesa portion 5a and the curable resin on the flange portion 5b are cured in the attached state (FIG. 6c), and the mesa portion 5a using the cured curable resins 44 and 45 or the metal-containing film 6 as a mask. The transferred substrate 5 is etched so that the metal-containing film 6 is removed and the metal-containing film 6 in the flange portion 5b remains (FIGS. 6d to f). Thereafter, for example, a mold 1 (that is, a double plate of the master mold 43) as shown in FIG. 6f can be obtained. In the present embodiment, the visibility of the auxiliary mark 30 is exhibited mainly by the metal-containing film 6 patterned on the flange portion 5b, as in the second embodiment.

(etching)
The etching of this embodiment is performed by the following two-stage etching, for example. The first etching is performed under conditions suitable for etching the metal-containing film 6 using the curable resin 44 as a mask, and the next etching is performed by etching the transferred substrate 5 using the processed metal-containing film 6 as a mask. Etching under conditions suitable for this. Then, if necessary, the curable resin is also removed. Such etching enables pattern transfer with higher accuracy.

  Examples of the mold manufacturing method according to the present invention will be described below.

(Production of master mold)
On the Si substrate, a resist solution containing a PHS (polyhydroxy styrene) -based chemically amplified resist as a main component was applied by spin coating to form a resist layer. Thereafter, while scanning the Si substrate on the XY stage, an electron beam modulated corresponding to a predetermined pattern was irradiated to expose the entire surface of the resist layer in a range of 10 mm square. Thereafter, the resist layer was developed, the exposed portion was removed, and selective etching was performed by RIE so that the groove depth became 100 nm using the pattern of the removed resist layer as a mask to obtain a Si mold. The mold surface was subjected to mold release treatment with OPTOOL DSX by a dip coating method.

  The concavo-convex pattern was formed in a 10 mm square region at the center of the Si substrate. The concavo-convex pattern is a line and space pattern having a length of 10 mm, a width of 50 nm, a pitch of 100 nm, and a depth of 100 nm.

(Transfer substrate)
A quartz substrate having a 152 mm square and a thickness of 6.35 mm was used as the substrate. First, a 10 mm square mesa portion having a height of 30 μm was formed by wet etching in the transferred region at the center of the substrate. Thereafter, the surface of the quartz substrate was subjected to surface treatment with KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silane coupling agent having excellent adhesion to the resist. Specifically, KBM-5103 was diluted to 1% by mass with PGMEA (propylene glycol monomethyl ether acetate) and applied to the substrate surface by spin coating. Subsequently, the coated substrate was annealed on a hot plate at 150 ° C. for 5 minutes to bond the silane coupling agent to the substrate surface.

(Metal-containing thin film)
A Cr film having a thickness of 30 nm was formed by sputtering to form a metal-containing thin film. In addition, a concavo-convex structure having a square lattice pattern in which dots of 1 μm square are arranged at a pitch of 2 μm was formed on the Cr film by using a general photolithography technique.

(Resist)
A resist containing 48% by mass of Compound A, 48% by mass of Aronix M220, 3% by mass of IRGACURE 379, and 1% by mass of Compound B was prepared.

(Resist application process)
A piezo inkjet printer, DMP-2838 manufactured by FUJIFILM Dimatix was used. DMC-11610, a dedicated 10 pl head, was used for the inkjet head. The discharge conditions were adjusted in advance so that the droplet amount was 10 pl. The droplet arrangement pattern was a staggered lattice with a droplet interval of 400 μm, and the droplets were arranged on the entire transfer region on the mesa in accordance with this droplet arrangement pattern. Further, the characters shown in FIG. 2 are drawn on the flange portion by dot arrangement.

(Nanoimprint method)
The master mold and the quartz substrate were brought close to a position where the gap was 0.1 mm or less, and these were aligned.

  Then, the space between the master mold and the quartz substrate was replaced with 99% by volume or more of He gas, and the pressure was reduced to 20 kPa or less after the He replacement. The master mold was brought into contact with droplets made of resist under reduced pressure He conditions.

After the contact, pressurization was performed for 5 seconds with a pressing pressure of 1 MPa, and exposure was performed with ultraviolet light including a wavelength of 360 nm so that an irradiation amount became 300 mJ / cm ² , thereby curing the resist.

  The outer edge part of the quartz substrate and the master mold was mechanically held, and the master mold was peeled from the resist by moving the quartz substrate or the master mold in a direction opposite to the pressing direction.

(Evaluation results)
The auxiliary mark obtained in the above example was inspected with a microscope. It was confirmed that characters could be easily distinguished at a magnification of 10 times.

DESCRIPTION OF SYMBOLS 1 Mold 2 Mold mesa part 2s Mold mesa part upper surface 3 Mold flange part 3s Mold flange part upper surface 5 Transfer substrate 5a Transfer substrate mesa part 5b Transfer substrate flange part 5c Transfer target substrate mesa part upper surface 5d Upper surface of flange portion 6 of substrate to be transferred 6 Metal-containing film 30 Auxiliary mark 40 Inkjet head 41, 42 Droplet 43 Master mold 43a Uneven pattern 44, 45 Cured curable resin

Claims (12)

In the method for producing a mold having a fine uneven pattern and an auxiliary mark on the surface,
Using a transfer substrate having a mesa structure including a mesa portion and a flange portion,
The plurality of droplets made of a curable resin are disposed on the mesa portion by a droplet discharge method, and the plurality of droplets made of a curable resin are disposed on the flange portion. Each of the plurality of droplets is lower than the height of the mesa portion and the plurality of droplets arranged on the flange portion are arranged to display the auxiliary marks,
Curing the curable resin on the mesa portion in a state in which the concave and convex pattern of the master mold is pressed against the plurality of droplets arranged on the mesa portion, and curing the curable resin on the flange portion;
A method for manufacturing a mold, comprising etching the substrate to be transferred using the cured curable resin as a mask.   The contact area between the droplet per droplet disposed on the flange portion and the flange portion is determined by the relationship between the droplet per mesa droplet disposed on the mesa portion and the mesa portion. The method for producing a mold according to claim 1, wherein the plurality of droplets are arranged so as to be larger than a contact area.   2. The plurality of droplets are arranged on the flange portion so that the width of the contact surface between the droplet and the flange portion for each droplet is 50 to 500 [mu] m. 2. A method for producing the mold according to 2.   Arrangement of the plurality of droplets such that a droplet amount per droplet disposed on the flange portion is larger than a droplet amount per droplet disposed on the mesa portion. The method for producing a mold according to claim 1, wherein:   5. The mold manufacturing method according to claim 1, wherein a substrate having a wettability on the surface of the flange portion larger than a wettability of the surface of the mesa portion is used as the substrate to be transferred.   The mold according to claim 5, wherein wettability of the flange portion is increased by a method of performing ultraviolet ozone treatment only on the flange portion or a method of forming a thin film having a high affinity with the curable resin. Manufacturing method.   The plurality of droplets are arranged such that a height of the droplets disposed on the flange portion is larger than a height of the droplets disposed on the mesa portion. The method for producing a mold according to any one of 1 to 6.   The method for producing a mold according to claim 1, wherein the plurality of droplets are disposed on the mesa portion and the plurality of droplets are disposed on the flange portion at the same time.   9. The etching according to claim 1, wherein the etching is performed so that the curable resin on the mesa portion is removed and the curable resin on the flange portion remains. Mold manufacturing method. The flange portion of the substrate to be transferred has a metal-containing film on at least a part of the surface of the flange portion;
The method for producing a mold according to any one of claims 1 to 8, wherein the plurality of droplets are arranged on the flange portion on the metal-containing film.   The method for producing a mold according to claim 10, wherein the metal-containing film has a fine uneven structure. The mesa portion of the substrate to be transferred has a metal-containing film on the surface of the mesa portion;
After the etching, using the curable resin or the metal-containing film as a mask, the metal-containing film in the mesa portion is removed and the metal-containing film in the flange portion remains. The method for producing a mold according to claim 10 or 11, wherein the substrate is etched.